| 90191-27-8

• 分子结构分类: 有机化合物 - 有机杂环化合物
• CAS: 90191-27-8
• 化学式: C₁₂H₂₀N₂*2F₆P
• 分子量: 482.233
• InChiKey: WOHJDCGQRNYREO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  21.0
• 可旋转键数：
  0.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  6.02
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  在 吡啶 、 tetramethylammonium borohydride 作用下， 生成 2,8-Diazatetracyclo<7.2.2.1^3,7.0^2,8>tetradecane
  参考文献：
  名称：

  Nucleophilic Cleavage Products from .beta.-Deprotonated Sesquidiazabicyclooctane Dication

  摘要：

  Nucleophilic cleavage of aminoaziridinium cation 2(+) by PhS(-), N=C-, CH3CO2-, and F- results in C-N+ bond cleavage with inversion at carbon, producing essentially only the axially-substituted (X) (22/31) derivatives for the latter two cases, but 40 and 15% exo-substituted 1(X) (22/22) are initially produced for thiophenoxide and cyanide, respectively. The increase in oxidation potential for 3(CN) vs 3 (0.22 V) is the same as that for replacement of the corresponding ii by CN in an acyclic system. X-ray structures show that larger changes in nitrogen pyramidality (Delta alpha(av) + 8.4 vs + 5.8 degrees) and NN distance (-0.172 vs -0.160 Angstrom) occur upon electron loss from 3 than from 1. Despite more constricted bond angles at nitrogen, crystalline 3(+)TsO(-) is more planar than 1(+)TsO(-) (alpha(av) = 119.1 degrees vs 118.6 degrees), and the two double nitrogen inversion forms of 3(+) are estimated to differ in energy by under 0.02 kcal/mol in solution from ENDOR and ESR studies. 3(0/+) shows slower self-electron transfer than 1(0/+) (k(ex) (25 degrees C, CH3CN) similar to 300 vs 700 M(-1) s(-1)). Neither more planar nitrogens for 3(+) than for 1(+) nor slower electron transfer for 3(0/+) are predicted by AM1 calculations.

  DOI：

  10.1021/jo00126a026
• 作为产物：
  描述：

  2,7-diazatetracyclo[6.2.2.2^3,6.0^2,7]tetradecane 在 nitrosyl hexafluorophosphate 作用下， 以 氘代乙腈 为溶剂， 生成
  参考文献：
  名称：

  Reactions of Bis(N,N'-bicyclic) Diazenium Dications

  摘要：

  Eleven bis(N,N'-bicyclic) diazenium dications were generated from the corresponding hydrazines by NOPF6 oxidation. Their reactivity depends greatly upon the sizes of the bicyclic rings. (We designate bicyclic ring size using the number of atoms in the two bridges in addition to the dinitrogen bridge all the compounds share.) Compounds with 21 rings alkylate acetonitrile at 240 K by opening a C-alpha-N+ bond to produce a trialkyldiazenium cation, with Delta G(double dagger) for the reaction increasing by at least 5.5 kcal/mol as the second bicyclic ring size increases. Compounds with an unsaturated bridge also alkylate acetonitrile; 22/u22(2+) only cleaves the u22 bridge and reacts faster than 21/22(2+), which only cleaves the 21 bridge. C-alpha-N+ cleavage of 22 and larger rings by acetonitrile has not been observed. 21/22(2+) is significantly more acidic than 22/22(2+), but both are beta-deprotonated by pyridine to produce aminoaziridinium cations at 240 K. At least mostly the exo 21 ring proton is lost from 21/22(2+). Dications with 23 and 24 bridges deprotonate at the alpha-carbon instead of the beta-carbon, and 22/23(2+) is slightly more kinetically acidic than 21/22(2+). 22/24(2+) is deprotonated rapidly by ether at 235 K.

  DOI：

  10.1021/jo00090a028

文献信息

• Nelsen, Stephen F.; Wang, Yichun, Journal of the American Chemical Society, 1991, vol. 113, # 15, p. 5905 - 5906
  作者：Nelsen, Stephen F.、Wang, Yichun

  DOI：——

  日期：——